CN102985447A - Polyurethane based photoinitiators - Google Patents
Polyurethane based photoinitiators Download PDFInfo
- Publication number
- CN102985447A CN102985447A CN2011800296448A CN201180029644A CN102985447A CN 102985447 A CN102985447 A CN 102985447A CN 2011800296448 A CN2011800296448 A CN 2011800296448A CN 201180029644 A CN201180029644 A CN 201180029644A CN 102985447 A CN102985447 A CN 102985447A
- Authority
- CN
- China
- Prior art keywords
- light trigger
- type light
- aggretion type
- alkyl
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004814 polyurethane Substances 0.000 title description 4
- 229920002635 polyurethane Polymers 0.000 title description 4
- -1 C3-C25 cycloalkyl Chemical group 0.000 claims description 56
- 125000000217 alkyl group Chemical group 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 28
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 25
- 150000002148 esters Chemical class 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 150000001408 amides Chemical class 0.000 claims description 18
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 18
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 17
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- 125000001072 heteroaryl group Chemical group 0.000 claims description 12
- 150000003457 sulfones Chemical class 0.000 claims description 12
- 239000012965 benzophenone Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 230000005855 radiation Effects 0.000 claims description 11
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 125000002252 acyl group Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- IDNUEBSJWINEMI-UHFFFAOYSA-N ethyl nitrate Chemical compound CCO[N+]([O-])=O IDNUEBSJWINEMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 150000002429 hydrazines Chemical class 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 150000003462 sulfoxides Chemical class 0.000 claims description 6
- 150000003568 thioethers Chemical class 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- PFLUPZGCTVGDLV-UHFFFAOYSA-N acetone azine Chemical compound CC(C)=NN=C(C)C PFLUPZGCTVGDLV-UHFFFAOYSA-N 0.000 claims description 4
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 4
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- SNVTZAIYUGUKNI-UHFFFAOYSA-N dibenzo[1,2-a:1',2'-e][7]annulen-11-one Chemical compound C1=CC2=CC=CC=C2C(=O)C2=CC=CC=C21 SNVTZAIYUGUKNI-UHFFFAOYSA-N 0.000 claims description 3
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000000269 nucleophilic effect Effects 0.000 claims description 3
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 claims description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims description 2
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 claims description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims description 2
- HYBVISCYJVVEDX-UHFFFAOYSA-N 4-(4-aminophenyl)-3-chloroaniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1Cl HYBVISCYJVVEDX-UHFFFAOYSA-N 0.000 claims description 2
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 claims description 2
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- WRUAHXANJKHFIL-UHFFFAOYSA-N benzene-1,3-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(S(O)(=O)=O)=C1 WRUAHXANJKHFIL-UHFFFAOYSA-N 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 2
- GKXVJHDEWHKBFH-UHFFFAOYSA-N xylylenediamine group Chemical group C=1(C(=CC=CC1)CN)CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 2
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 description 26
- 150000003254 radicals Chemical class 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000001723 curing Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 239000000017 hydrogel Substances 0.000 description 8
- 239000004970 Chain extender Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- 150000005215 alkyl ethers Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000003847 radiation curing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000005839 radical cations Chemical class 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- BMVWCPGVLSILMU-UHFFFAOYSA-N 5,6-dihydrodibenzo[2,1-b:2',1'-f][7]annulen-11-one Chemical compound C1CC2=CC=CC=C2C(=O)C2=CC=CC=C21 BMVWCPGVLSILMU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 238000006957 Michael reaction Methods 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- XBXFGOSIPGWNLZ-UHFFFAOYSA-N O=C1C=C(CC(C)(C)C1)C.N=C=O Chemical class O=C1C=C(CC(C)(C)C1)C.N=C=O XBXFGOSIPGWNLZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007031 hydroxymethylation reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000003211 polymerization photoinitiator Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- VNTDZUDTQCZFKN-UHFFFAOYSA-L zinc 2,2-dimethyloctanoate Chemical compound [Zn++].CCCCCCC(C)(C)C([O-])=O.CCCCCCC(C)(C)C([O-])=O VNTDZUDTQCZFKN-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polymerisation Methods In General (AREA)
- Polyethers (AREA)
Abstract
A photoinitiator of the general formula (I): (-(R1(A1)m)u-(R2(A2)n-0)0-(R3(A3)p-0)q-(R4(A4)r)v-C(0)NH-R5(A5)5-NHC(0))t- wherein R1( R2, R3, R4 and R5 and m, n, o, p, q, r, s, t, u and v are as defined herein and A1, A2, A3, A4 and A5 are identical or different photoinitiator moieties.
Description
Invention field
The present invention relates to the novel polymeric type light trigger based on poly alkyl ether-carbamate main chain.Light trigger partly is that side joint is on this main polymer chain.
Background of invention
Make coating curing and produce thus the coating that is used as gel (for example hydrogel) by ultraviolet ray (UV) radiation, this requires for the effective ways that cause the chemical reaction that causes this solidification process.Producing the free radical material by with the UV rayed time makes crosslinked being widely used in of polymer-based material make the hydrogel that is used for the medical apparatus coating.Usually use the coating composition that is cured as main component, with the UV radiation with polyvinylpyrrolidone and light trigger to produce hydrogel.The light trigger that uses in these methods can be oligomeric or polymerization.Oligomeric-type light trigger partly free diffusing makes these materials be exposed in the environment to the surface of the material that solidifies thus.
People such as EP 0 849 300, WO 2008/012325 and Weis (Wei), high-technology polymkeric substance (Polymers for Advanced Technologies), has disclosed the aggretion type light trigger at 12 phases of the 18th volume in 2008 in the 1763-1770 page or leaf.
Goal of the invention
The purpose of this invention is to provide the aggretion type light trigger, and be provided for the apparatus and method that UV solidifies these light triggers.
Summary of the invention
One aspect of the present invention provides the aggretion type light trigger of general primitive shown in a kind of Fig. 1 of having, and the system of deriving from the poly alkyl ether of the light trigger part of side joint on isocyanate moiety is provided particularly.
Therefore, aspect widely, the present invention relates to a kind of aggretion type light trigger with general formula I:
(-(R
1(A
1)
m)
u-(R
2(A
2)
n-O)
o-(R
3(A
3)
p-O)
q-(R
4(A
4)
r)
v–C(O)NH-R
5(A
5)
s-NHC(O))
t- (I)
In above chemical formula (I), R
2, R
3And R
5Can be independently selected from C1-C25 straight chained alkyl, C3-C25 branched-chain alkyl, C3-C25 cycloalkyl, aryl and heteroaryl, for example with the aromatic hydrocarbons up to 20 carbon atoms;
R
1And R
4To be selected from the C1-C25 straight chained alkyl independently of one another, the C3-C25 branched-chain alkyl, the C3-C25 cycloalkyl, aryl, heteroaryl, hydrogen,-OH,-CN, halogen, amine (for example-NR ' R "; wherein R' and R " are alkyl, C1-C25 alkyl suitably), acid amides (for example-CONR ' R " or R ' CONR "-, wherein R' and R " be alkyl, C1-C25 alkyl suitably); alcohol; ether; thioether; sulfone and its derivative; sulfonic acid and its derivative, sulfoxide and its derivative, carbonic ether, nitric ether, acrylate, hydrazine, azine, hydrazides, polyethylene, polypropylene, polyester, polymeric amide, polyacrylic ester, polystyrene, and urethane; And work as R
1And R
4When being alkyl and aryl, they can be replaced by one or more substituting groups, and these one or more substituting groups are selected from CN; OH; Trinitride; Ester; Ether; Acid amides (for example-and CONR ' R " or R ' CONR "-, wherein R ' and R " be alkyl, C1-C25 alkyl suitably); Halogen atom; Sulfone; Sulfonic acid; NH
2Or Nalk
2, wherein alk is any C
1-C
8Straight chained alkyl, C
3-C
8Side chain or cyclic alkyl;
M, n, p and r are from 0 to 10 real number independently, and s is the real number more than or equal to 1;
O and q are from 0 to 10000 real number independently, and its prerequisite is that o and q are all non-vanishing;
U and v are from 0 to 1 real number independently;
T is from 1 to 10000 integer; And
A
1, A
2, A
3, A
4And A
5It is identical or different light trigger part.
The further details of aggretion type light trigger of the present invention is provided in following dependent claims.
The present invention also provides a kind of method of making crosslinked substrate composition, said method comprising the steps of:
A., a kind of matrix polymer that is comprised of the aggretion type light trigger of following general formula I is provided:
(-(R
1(A
1)
m)
u-(R
2(A
2)
n-O)
o-(R
3(A
3)
p-O)
q-(R
4(A
4)
r)
v–C(O)NH-R
5(A
5)
s-NHC(O))
t- (I)
R wherein
2, R
3And R
5Can be selected from independently of one another C1-C25 straight chained alkyl, C3-C25 branched-chain alkyl, C3-C25 cycloalkyl, aryl and heteroaryl, for example with the aromatic hydrocarbons up to 20 carbon atoms;
R
1And R
4Be independently of one another be selected from C1-C25 straight chained alkyl, C3-C25 branched-chain alkyl, C3-C25 cycloalkyl, aryl, heteroaryl, hydrogen ,-OH ,-CN, halogen, amine, acid amides, alcohol, ether, thioether, sulfone and its derivative, sulfonic acid and its derivative, sulfoxide and its derivative, carbonic ether, isocyanic ester, nitric ether, acrylate, hydrazine, azine, hydrazides, polyethylene, polypropylene, polyester, polymeric amide, polyacrylic ester, polystyrene and urethane; And work as R
1And R
4When being alkyl and aryl, they can be replaced by one or more substituting groups, and these one or more substituting groups are selected from CN; OH; Trinitride; Ester; Ether; Acid amides; Halogen atom; Sulfone; Sulfonic acid; NH
2Or Nalk
2, wherein alk is any C
1-C
8Straight chained alkyl, C
3-C
8Side chain or cyclic alkyl;
M, n, p, r and s are from 0 to 10 real numbers, and its prerequisite is that the n+p+s sum is the real number greater than 0;
O and q are from 0 to 10000 real numbers;
U and v are from 0 to 1 real numbers;
T is from 1 to 10000 integer; And
A
1, A
2, A
3, A
4And A
5Identical or different light trigger part, and
B. be exposed to by the substrate composition that will obtain among the step a. and make its curing in the UV radiation.
The present invention relates to by this method obtainable crosslinked substrate composition.The present invention also provides according to aggretion type light trigger of the present invention for the purposes of solidifying a kind of substrate composition.
Brief description of drawingsfig
Fig. 1 has illustrated a general primitive of polymer-type light trigger, and wherein a plurality of light trigger part side joints are on a main polymer chain.
Fig. 2 has showed the curing of substrate composition, is afterwards to monitor G ' and G under 1Hz " along with the UV variation of open-assembly time.
Detailed description of the invention
The invention provides the aggretion type light trigger based on urethane.
Therefore the invention provides a kind of light trigger with following general formula I:
(-(R
1(A
1)
m)
u-(R
2(A
2)
n-O)
o-(R
3(A
3)
p-O)
q-(R
4(A
4)
r)
v–C(O)NH-R
5(A
5)
s-NHC(O))
t- (I)
R
2, R
3And R
5Can be selected from independently of one another C1-C25 straight chained alkyl, C3-C25 branched-chain alkyl, C3-C25 cycloalkyl, aryl and heteroaryl, for example with the aromatic hydrocarbons up to 20 carbon atoms.Suitably, R
2And R
3Be selected from independently of one another: C1-C25 straight chained alkyl, C3-C25 branched-chain alkyl, C3-C25 cycloalkyl are preferably the C1-C25 straight chained alkyl.R
5Can be selected from the group that C3-C25 cycloalkyl and aryl form.
R
1And R
4Be selected from independently of one another the C1-C25 straight chained alkyl, the C3-C25 branched-chain alkyl, the C3-C25 cycloalkyl, aryl, heteroaryl, hydrogen,-OH,-CN, halogen, amine (for example-NR ' R "; wherein R' and R " are alkyl, C1-C25 alkyl suitably), acid amides (for example-CONR ' R " or R ' CONR "-, wherein R' and R " be alkyl, C1-C25 alkyl suitably); alcohol; ether; thioether; sulfone and its derivative; sulfonic acid and its derivative, sulfoxide and its derivative, carbonic ether, isocyanic ester, nitric ether, acrylate, hydrazine, azine, hydrazides, polyethylene, polypropylene, polyester, polymeric amide, polyacrylic ester, polystyrene, and urethane.R
1And R
4Can be selected from independently of one another: C1-C25 straight chained alkyl, C3-C25 branched-chain alkyl, C3-C25 cycloalkyl.
R
1And R
4Can be with alcohol, ether, carbamate or amine groups, alternatively carry out end-functionalization with other nucleophilic groups at an end or two ends.Alternatively, R
1And R
4Can be considered to be derived from chainextender, wherein suitable chainextender can comprise quadrol, diethylenetriamine, Triethylenetetramine (TETA), propylene diamine, butanediamine, hexamethylene-diamine, the cyclohexyl diamines, piperazine, 2-methyl-piperazine, phenylenediamine, tolylene diamine, the xylylene diamines, three (2-aminoethyl) amine, 3,3 '-dinitrobenzene p-diaminodiphenyl, 4,4 '-methylene-bis (2-chloroaniline), 3,3 '-two chloro-4,4 '-benzidine, 2, the 6-diamino-pyridine, 4,4 '-diaminodiphenyl-methane, the menthane diamines, m-xylene diamine and isophorone diamine.
R
1And R
4Can also be selected from lower group, this group is comprised of the following: hydrazine; Azine is such as the acetone azine; The hydrazine that replaces, such as dimethylhydrazine, 1,6-hexa-methylene-two hydrazines and phosphinylidyne two hydrazines (carbohydrazine); The hydrazine class of dicarboxylic acid and sulfonic acid is such as hexanodioic acid list hydrazides or two hydrazides, oxalic acid two hydrazides, m-phthalic acid, two acyl traps, winestone acid dihydrazide, 1,3-phenylene disulfonic acid two acyl traps, omega-amino-caproic acid two hydrazides; By the hydrazides that lactone and hydrazine reaction are obtained, such as gamma-hydroxybutyric acid hydrazides, two-half carbon two acyl traps; The bishydrazide carbonic ether of glycol (in the glycol as mentioned above any).
Work as R
1And R
4When being alkyl and aryl, they can be replaced by one or more substituting groups, these substituting groups be selected from CN, OH, trinitride, ester, ether, acid amides (for example-CONR ' R " or R ' CONR "-, wherein R' and R " be alkyl, C1-C25 alkyl suitably), halogen atom, sulfone, sulfonic acid, NH
2Or Nalk
2, wherein alk is any C
1-C
8Straight chained alkyl, C
3-C
8Side chain or cyclic alkyl.
In the aggretion type light trigger with chemical formula (I), m, n, p and r are from 0 to 10 real number independently, and s is that real number more than or equal to 1 (that is, always exists A
5).In other words, the aggretion type light trigger that has a chemical formula (I) be following these: all isocyanate groups (R wherein
5) all comprise light trigger (namely in polymkeric substance, not having the isocyanate groups that does not contain light trigger).By light trigger partly is attached to isocyanate groups (R
5) in, can provide to comprise the still less substrate composition of component.
In the aggretion type light trigger with chemical formula (I), o and q are from 0 to 10000 real numbers, and its prerequisite is that o and q are all non-vanishing.
Suitably, o and q be from 0 to 5000, the real number of preferred 100-2000.
In the aggretion type light trigger with chemical formula (I), u and v are from 0 to 1 real number independently.Preferably u and v are the real number greater than zero independently.
In the aggretion type light trigger with chemical formula (I), t is from 1 to 10000 integer.Suitably, t be from 0 to 5000, the integer of preferred 100-2000.
In one embodiment, s is more than or equal to 1, means always to have at least one light trigger group on this isocyanic ester precursor.Alternatively or additionally, p can be more than or equal to 1, so there is at least one light trigger part in the repeating unit of each alkyl oxide section.The number that this permission light trigger partly exists and the additional flexibility of form aspect comprise two complementary light initiators possibility partly.N also can be more than or equal to 1, and this causes the repeating unit of each alkyl oxide section to have at least one light trigger part.Alternatively or additionally, r and v are more than or equal to 1, wherein r is R
4The R of each repeating unit that the light trigger number on the section and v are polyurethane chain
4(A
4)
rSection number, r can be zero, and m also can be zero.Be similar to r, m is R
1Light trigger number on the section.P and q can be more than or equal to 1.
Possible is that the m+n+p+r+s sum is 1.
Subscript o, m, n, o, p, q, r, s, v and u in general formula (I) represents a mean value/summation, and formula (I) represents multipolymer alternately, periodic, statistical/random, block and grafting thus.The example of random copolymers can be the nomenclature that is similar to formula I by application class, has formula (A
2B
1)
5Copolymer A BAAABABAABABAA.
An example of the identity (identity) of the formula I of a kind of aggretion type light trigger that is applied to describe among the present invention provides in scheme 1.
Scheme 1: the example that formula I is applied to a kind of light trigger.At this moment, formula I is expressed as (CH
2CH (CH
2OPhCOPh)
1O)
o(CH
2CH
2O)
1-C (O) NHC
6H
10CH (C
6H
4COPh) C
6H
10NHC (O))
tThen the value of o and t has determined the molecular weight of this light trigger.
Light trigger and light trigger part
In the aggretion type light trigger with chemical formula (I), A
1, A
2, A
3, A
4And A
5It is identical or different light trigger part.
In the present invention, light trigger is defined as a part that produces reactive specy (ion or free radical) and cause or several chemical reactions or conversion after absorb light.A preferred character of light trigger is overlapping well between UV light source light spectrum and the light trigger absorption spectrum.Overlapping or not overlapping minutely between the combination absorption spectrum of the intrinsic that another desirable characteristic is multiple other components in light trigger absorption spectrum and the substrate composition.
Suitably, these light trigger part side joints are on this polymkeric substance.This refers to that they are attached on the polymkeric substance at the some place that is different from polymer ends.
Light trigger of the present invention part can be (the Norrish I type) of cleavable or (the Norrish II type) of cleavable not independently.When exciting, the light trigger of cleavable part spontaneously resolves into two free radicals, and wherein the activity of at least one is enough to extract a hydrogen atom from most of matrix.Benzoin ether (comprising benzil dialkyl group ketal), phenyl hydroxyalkyl ketone and phenyl amino alkyl ketone are a plurality of important example of the light trigger part of cleavable.Light trigger of the present invention is effectively for making phototransformation from UV or visible light source become living radical, and these living radicals can extract hydrogen atom and other unsettled atoms and so realize covalent cross-linking from polymkeric substance.Randomly, amine, mercaptan and other electron donors can covalently boundly arrive the polymer-type light trigger or separately add or both.Be similar to hereinafter about the described mechanism of light trigger of cleavable not according to one, it is optional to add electron donor, but can strengthen the total efficiency of the light trigger of cleavable.
Suitably, light trigger of the present invention part all is (the Norrish II type) of cleavable not.As a reference, referring to for example A.Gilbert, J.Baggott: " Essentials of Molecular Photochemistry[molecular photochemistry is smart to be wanted] ", London Blackwell, 1991).The light trigger of cleavable part is not decomposed when exciting, and therefore the leaching from substrate composition provides possibility still less for small molecules.The light trigger of the not cleavable that excites can not resolve into free radical when exciting, but can extract a hydrogen atom from an organic molecule, or more effectively, extracts an electronics from a kind of electron donor (such as amine or mercaptan).Transfer transport produces a free radical anion and produces a radical cation at this electron donor at this light trigger.After this proton is transferred to this free radical anion to produce two uncharged free radicals from this radical cation; In these free radicals, the activity of the free radical on this electron donor is enough to extract a hydrogen atom from most of matrix.Benzophenone and relevant ketone (such as thioxanthone, xanthone, anthraquinone, Fluorenone, dibenzosuberenone, benzil and phenyl coumarin ketone) are the important example of the light trigger of cleavable not.Major part is put amine and a lot of mercaptan with a c h bond at the alpha-position of nitrogen-atoms and will be served as electron donor.Light trigger of the present invention part is cleavable not preferably.Using the advantage of the I I type different from I type light trigger is the less side products that produces in light-initiated reaction.Like this, be widely used benzophenone.When for example Alpha-hydroxy-alkyl-when benzene ketone (phenones) dissociates, form two kinds of free radicals in light-initiated reaction, they can further dissociate and may form loose combination, undesirable aromatic series by product.
From the light trigger part that causes within the scope of the present invention.When UV or excited by visible light, this photoinitiator is mainly by a kind of Norrish I type mechanism cracking and further crosslinked in the presence of without any conventional light trigger, thereby allows thick-layer to be cured.Recently, a kind of new classification based on the light trigger of beta-keto esters by (the Ashland Specialty Chemical of U.S. Ya Shilan fine chemicals company, USA) M.L Gu Erde (M.L Gould), S. Na Laiya-salad luxuriant and rich with fragrance (S.Narayan-Sarathy), T.E. Hammond (T.E.Hammond) and R.B. Fei Xiteer (R.B.Fechter) are in (2005): " the novel curable resin of UV that certainly causes: the 3rd generation (Novel Self-Initiating UV-Curable Resins:Generation Three) ", Europe radiation curing association can report 05(Proceedings from RadTech Europe 05), Barcelona, ESP (Barcelona, Spain), 18-20 day in October, 2005, the 1st volume, introduce in the 245-251 page or leaf, Vincent (Vincentz).Make ester form polyfunctional acrylic ester base catalysis Michael reaction (Michael addition) afterwards, form a kind of reticulation with many quaternary carbon atoms, each quaternary carbon atom has two adjacent carbonyls.
Another kind of based on maleimide from initiating system also by Ruan C.K. (C.K.Nguyen) of Ya Bao company (Albemarle Corporation) and Bei Di Allied Corp. (US) Law Department P.O. Box 2245R. Morristown, NJ 07960-2245, U.S. (Brady Associates LLC) (two companies all are the U.S.), W. rectify (W.Kuang) and C.A. shellfish enlightening (C.A.Brady) in (2003): " maleimide living oligomer (Maleimide Reactive Oligomers) ", Europe radiation curing association can report 03(Proceedings from RadTech Europe 03), Berlin, Germany (Berlin, Germany), 3-5 day in November, 2003, the 1st volume, the 589-94 page or leaf identifies in the Vincent (Vincentz).Mainly the light trigger of cleavable causes Raolical polymerizable to maleimide by serving as not, and simultaneously by adding free radical and spontaneously polymerization at the two keys of maleimide.In addition, the strong UV of maleimide is absorbed in this polymkeric substance and disappears, that is, maleimide is a kind of light trigger of photobleaching; This might make thick-layer solidify.
Therefore, in one embodiment of the invention, these light triggers partly comprise at least two dissimilar light trigger parts.Because the absorption peak of different light triggers preferably is in different wave length, so the total amount of the light that system absorbs increases.These different light triggers can be whole cleavables, all not cleavables or cleavable with the mixture of the light trigger of cleavable not.A kind of adulterant of several light trigger parts can represent collaborative characteristic, as with described in the Publication about Document, J.P. Han Er (J.P.Fouassier) not for example: " excited state of radical polymerization light trigger active (Excited-State Reactivity in Radical Polymerization Photoinitiators) ", the 1st chapter, the 1-61 page or leaf, " radiation curing in polymer science and the technology (Radiation curing in Polymer Science and technology) ", II rolls up (" light-initiated system (Photo-initiating Systems) ", not Han Er (J.P.Fouassier) and J.F. draw Bake (J.F.Rabek) to compile by J.P., London Ai Er Seville (Elsevier, London), 1993).In brief, multiple to [4, two (dimethylamino) benzophenone+benzophenone of 4'-], [benzophenone+2,4,6-tri-methyl benzophenone], effective energy of occurring in [thioxanthone+thiotolene base N-morpholinyl alkyl ketone] from a light trigger part to another light trigger shifts or transfer transport.
In addition; recently found that 2-hydroxyl-1-(4-(2-hydroxyl-oxethyl) phenyl)-2-methyl-prop-1-ketone (can trade(brand)name gorgeous good solid 2959(Irgacure 2959) is from buying on the market) be significantly higher than a kind of simple mixtures of these two kinds independent compounds with the efficiency of initiation of molecule 4-(4-Benzoylbenzene oxygen base oxethyl) the phenyl 2-hydroxyl-Raolical polymerizable that 2-propyl group ketone produces of the covalently bound formation of benzophenone; referring to (the Vienna University of Technology of technology university, Austria Vienna; Austria) S. rather (2005) of (S.Kopeinig) and R. Li Sika (R.Liska) of can wearing: " the further light trigger (Further Covalently Bonded Photoinitiators) of covalency bond "; Europe radiation curing association can report 05(Proceedings from RadTech Europe 05); Barcelona, ESP (Barcelona; Spain); 18-20 day in October, 2005; the 2nd volume; the 375-81 page or leaf, Vincent (Vincentz).This demonstrates, and different light triggers can show significant synergy partly in being present in same oligopolymer or polymkeric substance the time.
The light trigger of each type discussed above and light trigger part can be used as the light trigger part in polymer-type light trigger of the present invention.
In an embodiment of the light trigger that poly alkyl ether carbamate according to the present invention is derived, A
1, A
2, A
3, A
4And A
5It is identical or different light trigger part; these light triggers partly are selected from lower group, and this group is comprised of the following: benzoin ether, phenyl hydroxyalkyl ketone, phenyl amino alkyl ketone, benzophenone, thioxanthone, xanthone, dihydroketoacridine, anthraquinone, Fluorenone, dibenzosuberenone (dibenzosuberone), benzil, benzil ketals, α-dialkoxy-methyl phenyl ketone, Alpha-hydroxy-alkyl-phenyl ketone, alpha-amino group-alkyl-phenyl ketone, acyl group-phosphine oxide, phenyl coumarin ketone, silane, maleimide, with and derivative.This group can also be comprised of the derivative of these listed light trigger parts.
Suitably, A
1, A
2, A
3, A
4And A
5Be to be selected from lower group, this group is comprised of the following: st-yrax ethers, phenyl hydroxyalkyl ketone, phenylamino alkyl ketone, benzophenone, thioxanthene ketone, xanthone and their derivative.This group can also be comprised of the derivative of these listed light trigger parts.
Typically, A
1, A
2, A
3, A
4And A
5In at least one be the optional benzophenone part that replaces." optional replacement " in this article refers to this benzophenone partly by one or more radicals R
1Replace.
Polymer-type light trigger of the present invention
The light trigger that urethane is derived
These light triggers based on urethane can be by randomly making light trigger and vulcabond based on poly-trialkylphosphine oxide react synthetic with catalyzer, this catalyzer is for example pink salt, organotin ester, such as dibutyltin dilaurate or tertiary amine such as triethyl diamines, N, N, N ', N '-tetramethyl--1,3-butane diamines or generally acknowledge to be used in the art other catalyzer of urethane reaction.Other example is: stannous octoate, triethylamine, (dimethyl aminoethyl) ether, morpholinium compound such as β, the carboxylate salt of β '-dimorpholine base Anaesthetie Ether, bismuth, zinc bismuth carboxylate salt (for example from leading chemical company (Shephard chemicals) BICAT catalyzer), iron(ic) chloride (III), potassium octanoate, potassium acetate and DABCO(diazabicylo [2.2.2] octane), also and the 2-ethyl is sad and the mixture of stannous octoate.Mentioned catalyzer can also combination with one another use, and typically its value is 5 to 200 1,000,000/portions of the gross weight of prepolymer reactant.Describe in scheme 2 for the synthesis of the illustrative methods based on the light trigger of urethane.
Scheme 2: for the preparation of the illustrative methods based on the light trigger of urethane.
The isocyanic ester of describing in the scheme 2 is (4-(two-(4-cyclic isocyanate hexyl) methyl) phenyl) (phenyl) ketone.Can use various other isocyanic ester, comprise the α with 5 to 20 carbon atoms, ω-alkylidene group vulcabond, the two isocyanic acid tetramethylene esters that replace of light trigger for example, two isocyanic acid hexa-methylene esters, two isocyanic acid tri-methyl hexamethylene esters, two isocyanic acid isophorone esters, the diethylbenzene vulcabond, 1,10-two isocyanic acid decamethylene esters, tetrahydrobenzene 1,2-vulcabond and tetrahydrobenzene 1, the 4-vulcabond, 1,12-dodecane vulcabond, the 2-methyl isophthalic acid, 5-pentylidene and aromatic isocyanate, such as 2,4-and 2,6-toluylene group diisocyanate, 4, the 4-'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, the dianisidine vulcabond, the tolidine vulcabond, two (4-cyclic isocyanate hexyl) methane, the in addition polymeric polyisocyanate of polymer-type, such as the neo-pentyl tetraisocyanate, m-xylylene vulcabond, naphthane-1,5 vulcabond, and two (4-isocyanic acid phenyl) methane.
The end group that exists on the light trigger based on urethane depends on the stoichiometry of these reactants.If the end group of for example supposing this polymkeric substance is free hydroxyl group, then should uses and compare excessive poly alkyl ether reactant with the amount of isocyanic ester.On the other hand, if free isocyanate groups group should exist as end group, then should use excessive isocyanic ester.
It is also contemplated that and use more than a kind of poly alkyl ether light trigger part as reactant.
Other are based on light triggers of urethane report to some extent in the literature, for example at J.Wei, H.Wang, X.Jiang, J.Yin, Macromolecules[macromole], 40 (2007), the urethane that the benzophenone in 2344-2351) is derived.An example of this light trigger provides in scheme 3.
Scheme 3: at J.Wei, H.Wang, X.Jiang, J.Yin, Macromolecules[macromole], 40 (2007), the aggretion type of describing in 2344-2351), synthetic based on the light trigger of urethane.
An attractive especially characteristic of the coating composition that the light trigger of only being derived by urethane forms is, compares the extra physical crosslinking that is caused by these carbamate sections with the aggretion type light trigger that does not for example have the hydrogen bond possibility.This extra physical crosslinking meeting so that these based on the light trigger of poly alkyl ether carbamate with compare in producing the process of hydrogel for example more effectively based on the light trigger of poly alkyl ether, and meeting is so that they are thermoplastic.
The example based on the light trigger of urethane with characteristic described above is depicted in the scheme 4.
Scheme 4: the light trigger of deriving with N-methyl-diethanolamine, vulcabond and polyoxyethylene glycol comes synthesized polymer type light trigger as parent material
Use following total chemical formula:
(-(R
1(A
1)
m)
u-(R
2(A
2)
n-O)
o-(R
3(A
3)
p-O)
q-(R
4(A
4)
r)
v–C(O)NH-R
5(A
5)
s-NHC(O))
t-，
Polymkeric substance can be write as shown in the scheme 4:
(-OCH
2CH
2N(CH
3)CH
2CH
2O)
u-(OCH(CH
2OPhCOAr)
1CH
2O)
n-C(O)NH-C
6H
10CH(PhCOPh)C
6H
10NHC(O)-)
t
This example has represented the general method that will be attached to by the light trigger that diethanolamine replaces in the urethane.
Exist some additive methods for the synthesis of the light trigger based on urethane, some important method are pointed out below:
At first, by being reacted, light trigger poly alkyl ether and isocyanic ester and one or more possible chainextenders form isocyanate-terminated prepolymer.Being characterized as of this type of prepolymer has isocyanate groups and/or alcohol, amine or other nucleophilic functional group as the end group in the polymkeric substance.In addition, this prepolymer has the molecular weight less than target urethane light trigger.These prepolymers can form in the situation of not using catalyzer, yet the catalyzer that is selected from some cases in the above catalyzer may be preferred.Have at this prepolymer in the situation of carboxyl of side joint, the optional neutralization of this prepolymer can produce the carboxylate anion, therefore has solvability or the dispersibility of increase in water.Such neutralizing agent comprises: tertiary amine, metal hydroxides, ammonium hydroxide, phosphuret-(t)ed hydrogen and other reagent well known to those skilled in the art.Tertiary amine and ammonium hydroxide are preferred, for example triethylamine, dimethylethanolamine, N-morpholine and analogue and its mixture.Will be appreciated that and can replace tertiary amine with primary amine or secondary amine, if they fully be obstructed, in order to avoid interference to the chain extension process.Then can process to form the urethane light trigger of describing among the present invention to this prepolymer, this be by
(1) with emulsifying agent (external emulsifying agent, such as tensio-active agent, or inner emulsifying agent, have anionic group and/or cation group as the part of polyurethane backbone or side joint thereon, and/or as the end group on the polyurethane backbone) by shearing force this prepolymer is disperseed.
(2) acetone method wherein forms a kind of prepolymer in the situation of other polar solvents that do not have or exist acetone, methyl ethyl ketone and/or nonreactive and easy distillation.Necessary, with this prepolymer in the solvent of mentioning before further distillation and with before the chainextender mentioned further carry out chain extension.Water is added through distilling in the urethane of chain extension and with solvent.Change to this method is in order to be scattered in the water at this prepolymer after it to be carried out chain extension.
(3) melting dispersion method wherein forms a kind of isocyanate-terminated prepolymer, and then makes itself and excess of ammonia or urea react to form to have the low-molecular-weight oligopolymer of terminal urea or biuret group.This oligopolymer is dispersed in water and carries out chain extension by the hydroxymethylation of biuret group and formaldehyde.
(4) ketazine and ketimine process make hydrazine or diamines and reactive ketone and form ketazine and ketoimine.These are added in a kind of prepolymer and remain for isocyanic ester is inertia.Because this prepolymer is scattered in the water, hydrazine or diamines are released, and chain extension occurs when disperseing to occur.
(5) continuous processing polymerization has wherein formed a kind of isocyanate-terminated prepolymer.One or more high shear mixing heads are passed in this prepolymer pumping and be distributed in the water, then carry out chain extension at described one or more mixing heads place, perhaps disperse simultaneously and chain extension at aforementioned one or more mixing heads place.This is to finish by a plurality of a fluid streams that are comprised of prepolymer (or the prepolymer that neutralized), the neutralizing agent of choosing wantonly, water and the chainextender of choosing wantonly and/or tensio-active agent.
(6) backward feed valve wherein under agitation is filled into water and one or more optional neutralizing agent and/or one or more chainextender amine in this prepolymer.This prepolymer can neutralize before adding water and/or diamines type chainextender.
(7) solution polymerization.
(8) mass polymerization includes but not limited to extrusion molding.
In the present invention, use M
w(weight-average molecular weight) characterizes these aggretion type light triggers.The efficient of this aggretion type light trigger and this light trigger and these one or more form the polymkeric substance of gel or monomer blending how good relevant.The molecular weight that this light trigger is arranged among the important parameter in this regard.Too high molecular weight does not allow the good easy Combination between other components of aggretion type light trigger and this substrate composition.Particularly, be significantly different if this aggretion type light trigger forms chemical property and the molecular weight of the polymkeric substance of gel from these one or more, the easy Combination that then obtains is poor, this so that cause substrate composition to be difficult to solidify.
Therefore in one embodiment, the weight-average molecular weight that light trigger according to the present invention suitably has is between 0.2kDa and 100kDa, more preferably between 0.2kDa and 75kDa, preferably between 0.5kDa and 50kDa.Suitably, the weight-average molecular weight of this light trigger is 0.5-40kDa, and the lifting capacity of benzophenone part is greater than 0% and is lower than 50%.
Example 2 is examples that (obtaining from example 1) urethane are cured for the purpose that produces hydrogel.Sample (see figure 2) after the curing is hydrogel precursor, this means to be exposed in water or the water-based swelling medium by the sample after will solidifying to have obtained hydrogel.The molecular weight of the polymkeric substance of example 1 is 43kD.
Solidify
By being exposed to the UV radiation, substrate composition of the present invention makes its curing.
Curing can be carried out under melt state or in solution.The latter comprises a plurality of steps, this substrate composition is dissolved in a kind of suitable solvent and for example sprays on the pipe, and is exposed to subsequently in the UV radiation in these steps.Can be evaporated or be retained in the coating and as a kind of swelling medium of desirable gel that provides after this solvent and work.
Ultraviolet spectrogram is divided into A, B and C section, and wherein UV A extends to 315nm from 400nm, and UV B extends to 280nm from 315nm, and UV C extends to 100nm from 280nm.Light source by using one to produce the light of wavelength in visible region (400 to 800nm) obtains some advantages aspect curing depth, condition is that light trigger can successfully make material cured under these wavelength.Specifically, scattering phenomenon is not too obvious under long wavelength more, therefore produces a larger penetration depth in material.Therefore, focus on the light trigger that absorbs and can induce curing under the longer long wavelength.By the substituting group on these aromatic series parts of choose reasonable, the to a certain extent red shift of the absorption spectrum of polymer-type light trigger then will promote the curing of relatively large depth.
Can also come solidified sample with multiphoton absorption, the wavelength of the light source of use emission is to solidify the twice of required optical wavelength or even many times in the single photon method.For example, absorb maximum value can be used in the light source of launching at about 500nm place at the composition of the light trigger at about 250nm place and be cured by two-photon absorption method a kind of having comprised, and prerequisite is that this biabsorption cross section is sufficiently high.The solidification process that multi-photon causes can also help the greater room resolving power for the area that solidifies, and this is illustrated in nature 412 (2001), in 697, has wherein formed the 3D structure by the two-photon solidification method.
In the present invention, solidify initially by substrate composition being exposed to high-energy radiation, preferably causing under the UV light.This light-initiated process is by carrying out radiation and carry out with lamp or the UV radiation of wavelength region from 250 to 500nm by described above and known method itself.Operable source of radiation has sunlight or artificial lamp or laser.For example, high pressure, middle pressure or low pressure mercury lamp and xenon and tungsten lamp are favourable.Similarly, excimer laser apparatus, solid laser and be favourable based on the laser apparatus of diode.Even can think that pulsed laser system also is applicable to the present invention.Light source based on diode is favourable for initiating chamical reaction generally.
In this solidification process, this aggretion type light trigger makes this matrix polymer transform in light-initiated chemical process.
Automatically solidify
Although polymer-type light trigger described herein can promote a kind of curing of matrix on every side, but because these light triggers itself are polymkeric substance, so they can also " solidify " automatically, mean that these polymer-type light triggers can only consist of a kind of coating composition that is cured with the UV irradiation.Work as A
1, A
2, A
3, A
4And A
5In at least one this is correlated with especially when being the optional benzophenone part that replaces.
Therefore in one aspect, the invention provides a kind of method of making crosslinked substrate composition, said method comprising the steps of:
A., a kind of matrix polymer that is comprised of the aggretion type light trigger of following general formula I is provided:
(-(R
1(A
1)
m)
u-(R
2(A
2)
n-O)
o-(R
3(A
3)
p-O)
q-(R
4(A
4)
r)
v–C(O)NH-R
5(A
5)
s-NHC(O))
t- (I)
R wherein
2, R
3And R
5Can be selected from independently of one another C1-C25 straight chained alkyl, C3-C25 branched-chain alkyl, C3-C25 cycloalkyl, aryl and heteroaryl, for example with the aromatic hydrocarbons up to 20 carbon atoms;
R
1And R
4Be independently of one another be selected from C1-C25 straight chained alkyl, C3-C25 branched-chain alkyl, C3-C25 cycloalkyl, aryl, heteroaryl, hydrogen ,-OH ,-CN, halogen, amine, acid amides, alcohol, ether, thioether, sulfone and its derivative, sulfonic acid and its derivative, sulfoxide and its derivative, carbonic ether, isocyanic ester, nitric ether, acrylate, hydrazine, azine, hydrazides, polyethylene, polypropylene, polyester, polymeric amide, polyacrylic ester, polystyrene and urethane; And work as R
1And R
4When being alkyl and aryl, they can be replaced by one or more substituting groups, and these one or more substituting groups are selected from CN; OH; Trinitride; Ester; Ether; Acid amides; Halogen atom; Sulfone; Sulfonic acid; NH
2Or Nalk
2, wherein alk is any C
1-C
8Straight chained alkyl, C
3-C
8Side chain or cyclic alkyl;
M, n, p, r and s are from 0 to 10 real numbers, and its prerequisite is that the n+p+s sum is the real number greater than 0;
O and q are from 0 to 10000 real numbers;
U and v are from 0 to 1 real numbers;
T is from 1 to 10000 integer; And
A
1, A
2, A
3, A
4And A
5Identical or different light trigger part, and
B. be exposed to by the substrate composition that will obtain among the step a. and make its curing in the UV radiation.
The invention provides by the obtainable crosslinked substrate composition of aforesaid method.
Should " automatically solidify " method suitably is to carry out (that is, not having intermediate steps) with step a. and b. order directly adjacent to each other.Aspect of this " automatically solidifying " method, the method only is comprised of step a. and b..
The advantage that a kind of one-component system (as being provided by this " automatically solidifying " method) provides is that these aggretion type light triggers are thermoplastic.Like this, their the more not viscosity that under higher shearing rate, becomes, thus they are processed in extrusion easilier.By contrast, for example polyvinylpyrrolidone can not be extruded.Provide the light trigger that is suitable in " automatically solidifying " method in all details of the aggretion type light trigger that this provides and the purpose that structure is refined.
In addition, what aggretion type light trigger that should " automatically solidify " method consisted of this substrate composition only has a component, that is, this substrate composition can be comprised of the aggretion type light trigger.This advantage that provides is to avoid additive (for example softening agent, viscosity modifier), has reduced thus to leach from crosslinked substrate composition the chance of lower-molecular-weight component.
Gel state
Swelling properties is a kind of material of swellable, yet can not be dissolved in this swelling medium.Hydrogel refers to the main material that is made of material water dissolvable or water-swellable.Gelatinous mass is being characterized aspect its rheological property and under its drying regime.Particularly, characterize the mechanical characteristics (T.G.Mezger: " The Rheology Handbook[rheology handbook] ", Vincentz Network, Hannover, 2006) of these materials with storage modulus and out-of-phase modulus.As described above, be to monitor G ' (ω) and G after the curing of substrate composition " (ω) along with the UV variation of open-assembly time.At the example of the present invention that is used for explanation, survey rheological properties and further in test process, sample is heated to 120 ° of C with the frequency of 1Hz.
The invention still further relates to a kind of via the obtainable gel of method described herein.
Example 1
(4-((two-(2-hydroxyethyl) amino) methyl) phenyl) (phenyl) ketone (0.04g, 0.13mmol) and PEG2000(1.7g, 0.85mmol packs in the two neck flasks of a 50mL).Until stopping (about 5 minutes of 80 ° of C), all bubbling phenomenons come from reaction flask, to remove moisture by melting reaction thing under vacuum and with liquid reaction mixture heating.Allow this flask under vacuum, to cool off, wash away to its assembling reflux exchanger and with nitrogen.Add dry chlorobenzene (10mL) and reaction mixture is stirred to obtain uniform settled solution at 60 ° of C.Add 4 by syringe, 4 '-methylene-bis (cyclic isocyanate polyhexamethylene) (0.26g, 0.99mmol) and with reaction mixture under refluxing heating 48-60h until 145 ° of C.(50mL) and evaporate to dryness are cooled off, diluted to this stickiness yellow mixture at ambient temperature in toluene.Add methyl alcohol (125mL) and water (75mL) in the residue and the turbid solution of stickiness is provided.The evaporation of this mixture has provided the gumminess solid, with its under vacuum at the dry 4-6h of 75 ° of C, obtain faint yellow solid with almost quantitative productive rate (1).M
w 43kDa，PD=2.4。
Example 2
To be placed on from the flat globe (oblate) of the original polymer of example 1 that distance between (parallel plate configuration, base plate are quartz glass plate) between two plates of a rheometer and this two plates is set as 0.3mm and temperature is 120 ° of C.Measurement is to operate under 1% fixing strain and a constant frequency 1Hz.When out-of-phase modulus and storage modulus have been stablized, turn on a UV lamp, pass base plate irradiation sample on the rheometer via a fiber of lamp thus.When UV light irradiation sample, out-of-phase modulus and storage modulus be time to time change then.The displaying result of these measurements has been shown among Fig. 1.Sample in being exposed to UV the time its solids content increase reducing and can find out from tan δ.The increase of tan δ is signifying the increase of the amount of liquid that exists in the sample.
Claims (23)
1. aggretion type light trigger with following general formula I:
(-(R
1(A
1)
m)
u-(R
2(A
2)
n-O)
o-(R
3(A
3)
p-O)
q-(R
4(A
4)
r)
v–C(O)NH-R
5(A
5)
s-NHC(O))
t- (I)
R wherein
2, R
3And R
5Can be selected from independently of one another C1-C25 straight chained alkyl, C3-C25 branched-chain alkyl, C3-C25 cycloalkyl, aryl and heteroaryl, for example with the aromatic hydrocarbons up to 20 carbon atoms;
R
1And R
4Be independently of one another be selected from C1-C25 straight chained alkyl, C3-C25 branched-chain alkyl, C3-C25 cycloalkyl, aryl, heteroaryl, hydrogen ,-OH ,-CN, halogen, amine, acid amides, alcohol, ether, thioether, sulfone and its derivative, sulfonic acid and its derivative, sulfoxide and its derivative, carbonic ether, nitric ether, acrylate, hydrazine, azine, hydrazides, polyethylene, polypropylene, polyester, polymeric amide, polyacrylic ester, polystyrene and urethane; And work as R
1And R
4When being alkyl and aryl, they can be replaced by one or more substituting groups, and these one or more substituting groups are selected from CN; OH; Trinitride; Ester; Ether; Acid amides; Halogen atom; Sulfone; Sulfonic acid; NH
2Or Nalk
2, wherein alk is any C
1-C
8Straight chained alkyl, C
3-C
8Side chain or cyclic alkyl;
M, n, p and r are from 0 to 10 real number independently, and s is the real number more than or equal to 1;
O and q are from 0 to 10000 real number independently, and its prerequisite is that o and q are all non-vanishing;
U and v are from 0 to 1 real number independently;
T is from 1 to 10000 integer; And
A
1, A
2, A
3, A
4And A
5It is identical or different light trigger part.
2. aggretion type light trigger according to claim 1, its, R
1And R
4Be with alcohol, ether, carbamate or amine groups, alternatively carry out end-functionalization with other nucleophilic groups at an end or two ends.
3. according to each described aggretion type light trigger in the above claim, wherein, R
1And R
4To be selected from lower group, this group is comprised of the following: quadrol, diethylenetriamine, Triethylenetetramine (TETA), propylene diamine, butanediamine, hexamethylene-diamine, cyclohexyl diamines, piperazine, 2-methyl-piperazine, phenylenediamine, tolylene diamine, xylylene diamines, three (2-aminoethyl) amine, 3,3 '-dinitrobenzene p-diaminodiphenyl, 4,4 '-methylene-bis (2-chloroaniline), 3,3 '-two chloro-4,4 '-benzidine, 2,6-diamino-pyridine, 4,4 '-diaminodiphenyl-methane, menthane diamines, m-xylene diamine and isophorone diamine.
4. aggretion type light trigger according to claim 1, wherein, R
1And R
4Be to be selected from lower group, this group is comprised of the following: hydrazine; Azine is such as the acetone azine; The hydrazine that replaces, such as dimethylhydrazine, 1,6-hexa-methylene-two hydrazines and phosphinylidyne two hydrazines; The hydrazine class of dicarboxylic acid and sulfonic acid is such as hexanodioic acid list hydrazides or two hydrazides, oxalic acid two hydrazides, m-phthalic acid, two acyl traps, winestone acid dihydrazide, 1,3-phenylene disulfonic acid two acyl traps, omega-amino-caproic acid two hydrazides; By the hydrazides that lactone and hydrazine reaction are obtained, such as gamma-hydroxybutyric acid hydrazides, two-half carbon two acyl traps; The bishydrazide carbonic ether of glycol.
5. each described aggretion type light trigger, wherein R according to claim 1-2
1And R
4To be selected from independently of one another: C1-C25 straight chained alkyl, C3-C25 branched-chain alkyl and C3-C25 cycloalkyl.
6. according to each described aggretion type light trigger in the above claim, wherein, R
5To be selected from the group that C3-C25 cycloalkyl and aryl form.
7. according to each described aggretion type light trigger, wherein R in the above claim
2And R
3To be selected from independently of one another: C1-C25 straight chained alkyl, C3-C25 branched-chain alkyl and C3-C25 cycloalkyl, preferred C1-C25 straight chained alkyl.
8. according to each described aggretion type light trigger in the above claim, wherein, A
1, A
2, A
3, A
4And A
5In at least one be the optional benzophenone part that replaces.
9. according to each described aggretion type light trigger, wherein A in the above claim
1, A
2, A
3, A
4And A
5Be to be selected from lower group, this group is comprised of the following: benzoin ether, phenyl hydroxyalkyl ketone, phenyl amino alkyl ketone, benzophenone, thioxanthone, xanthone, dihydroketoacridine, anthraquinone, Fluorenone, dibenzosuberenone, benzil, benzil ketals, α-dialkoxy-methyl phenyl ketone, Alpha-hydroxy-alkyl-phenyl ketone, alpha-amino group-alkyl-phenyl ketone, acyl group-phosphine oxide, phenyl coumarin ketone, silane, maleimide, with and derivative.
10. according to each described aggretion type light trigger in the above claim, wherein, A
1, A
2, A
3, A
4And A
5Be to be selected from lower group, this group is comprised of the following: st-yrax ethers, phenyl hydroxyalkyl ketone, phenyl amino alkyl ketone, benzophenone, thioxanthene ketone, xanthone and their derivative.
11. according to each described aggretion type light trigger in the above claim, wherein the weight-average molecular weight that has of this aggretion type light trigger is between 0.2kDa and 100kDa, preferably between 0.2kDa and 75kDa, more preferably between 0.5kDa and 50kDa.
12. according to each described aggretion type light trigger in the above claim, wherein, the weight-average molecular weight of this aggretion type light trigger is 0.5-40kDa, and the lifting capacity of benzophenone part is greater than 0% and is lower than 50%.
13. according to each described aggretion type light trigger in the above claim, wherein o and q are 1-5000, the real number of 100-2000 preferably independently.
14. according to each described aggretion type light trigger in the above claim, wherein t be 1 to 5000, the integer of preferred 100-2000.
15. according to each described aggretion type light trigger in the above claim, wherein the m+n+p+r+s sum is 1.
16. according to each described aggretion type light trigger in the above claim, wherein, s is greater than 1.
17. according to each described aggretion type light trigger in the above claim, wherein, r and v are all greater than 0.
18. each described aggretion type light trigger according to claim 1-16, wherein r is zero.
19. according to each described aggretion type light trigger in the above claim, wherein m is zero.
20. according to each described aggretion type light trigger in the above claim, wherein, p and q are all greater than 0.
21. the method for the manufacture of crosslinked substrate composition said method comprising the steps of:
A., a kind of matrix polymer that is comprised of the aggretion type light trigger of following general formula I is provided:
(-(R
1(A
1)
m)
u-(R
2(A
2)
n-O)
o-(R
3(A
3)
p-O)
q-(R
4(A
4)
r)
v–C(O)NH-R
5(A
5)
s-NHC(O))
t- (I)
R wherein
2, R
3And R
5Can be selected from independently of one another C1-C25 straight chained alkyl, C3-C25 branched-chain alkyl, C3-C25 cycloalkyl, aryl and heteroaryl, for example with the aromatic hydrocarbons up to 20 carbon atoms;
R
1And R
4Be independently of one another be selected from C1-C25 straight chained alkyl, C3-C25 branched-chain alkyl, C3-C25 cycloalkyl, aryl, heteroaryl, hydrogen ,-OH ,-CN, halogen, amine, acid amides, alcohol, ether, thioether, sulfone and its derivative, sulfonic acid and its derivative, sulfoxide and its derivative, carbonic ether, isocyanic ester, nitric ether, acrylate, hydrazine, azine, hydrazides, polyethylene, polypropylene, polyester, polymeric amide, polyacrylic ester, polystyrene and urethane; And work as R
1And R
4When being alkyl and aryl, they can be replaced by one or more substituting groups, and these one or more substituting groups are selected from CN; OH; Trinitride; Ester; Ether; Acid amides; Halogen atom; Sulfone; Sulfonic acid; NH
2Or Nalk
2, wherein alk is any C
1-C
8Straight chained alkyl, C
3-C
8Side chain or cyclic alkyl;
M, n, p, r and s are from 0 to 10 real numbers, and its prerequisite is that the n+p+s sum is the real number greater than 0;
O and q are from 0 to 10000 real numbers;
U and v are from 0 to 1 real numbers;
T is from 1 to 10000 integer; And
A
1, A
2, A
3, A
4And A
5Identical or different light trigger part, and
B. be exposed to by the substrate composition that will obtain among the step a. and make its curing in the UV radiation.
22. one kind by the obtainable crosslinked substrate composition of the described method of claim 21.
23. each described aggretion type light trigger is for the purposes of solidifying a kind of substrate composition according to claim 1-20.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DKPA201070282 | 2010-06-22 | ||
| DKPA201070282 | 2010-06-22 | ||
| DKPA201070342 | 2010-07-27 | ||
| DKPA201070342 | 2010-07-27 | ||
| DKPA201070572 | 2010-12-22 | ||
| DKPA201070572 | 2010-12-22 | ||
| DKPA201170305 | 2011-06-16 | ||
| DKPA201170305 | 2011-06-16 | ||
| PCT/DK2011/050225 WO2011160637A2 (en) | 2010-06-22 | 2011-06-22 | Polyurethane based photoinitiators |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102985447A true CN102985447A (en) | 2013-03-20 |
Family
ID=44509884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800296448A Pending CN102985447A (en) | 2010-06-22 | 2011-06-22 | Polyurethane based photoinitiators |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20130096224A1 (en) |
| EP (1) | EP2585493A2 (en) |
| JP (1) | JP2013529692A (en) |
| CN (1) | CN102985447A (en) |
| BR (1) | BR112012032050A2 (en) |
| RU (1) | RU2013102587A (en) |
| SG (1) | SG186419A1 (en) |
| WO (1) | WO2011160637A2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG183124A1 (en) | 2010-02-23 | 2012-09-27 | Coloplast As | Polymeric photoinitiators |
| CN102947350A (en) * | 2010-06-22 | 2013-02-27 | 科洛普拉斯特公司 | Skin-friendly adhesives from polyalkylether-based photoinitiators |
| US9464143B2 (en) * | 2010-06-22 | 2016-10-11 | Coloplast A/S | Grafted photoinitiators |
| RU2584165C2 (en) * | 2010-11-12 | 2016-05-20 | Колопласт А/С | New polymer photo initiators |
| DK2638078T3 (en) * | 2010-11-12 | 2015-04-20 | Coloplast As | NEW WAYS TO POLYACRYLATES |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4691059A (en) * | 1985-08-30 | 1987-09-01 | Minnesota Mining And Manufacturing Company | Copolymerizable UV stabilizers |
| CA2034274A1 (en) * | 1990-02-07 | 1991-08-08 | James A. Bonham | Polymers containing halomethyl-1,3,5-triazine moieties |
| US5459222A (en) * | 1993-06-04 | 1995-10-17 | Ciba-Geigy Corporation | UV-absorbing polyurethanes and polyesters |
| EP0849300A1 (en) | 1996-12-19 | 1998-06-24 | Basf Aktiengesellschaft | Polyurethanes with covalently bound photoinitiator-units |
| US7157535B2 (en) * | 2002-06-19 | 2007-01-02 | National Starch And Chemical Investment Holding Corporation | Polymeric photoinitiators |
| US20070004815A1 (en) * | 2005-06-30 | 2007-01-04 | Ashland Licensing And Intellectual Property Llc | Self-photoinitiating multifunctional urethane oligomers containing pendant acrylate groups |
| EP2049172B1 (en) | 2006-07-25 | 2014-12-31 | Coloplast A/S | Photo-curing of thermoplastic coatings |
| WO2008071796A1 (en) * | 2006-12-15 | 2008-06-19 | Coloplast A/S | Coatings prepared from poly(ethylene oxide) and photo-initator-containing scaffolds |
| SG183124A1 (en) * | 2010-02-23 | 2012-09-27 | Coloplast As | Polymeric photoinitiators |
-
2011
- 2011-06-22 CN CN2011800296448A patent/CN102985447A/en active Pending
- 2011-06-22 JP JP2013515700A patent/JP2013529692A/en not_active Withdrawn
- 2011-06-22 EP EP11731246.2A patent/EP2585493A2/en not_active Withdrawn
- 2011-06-22 RU RU2013102587/04A patent/RU2013102587A/en not_active Application Discontinuation
- 2011-06-22 BR BR112012032050A patent/BR112012032050A2/en not_active Application Discontinuation
- 2011-06-22 SG SG2012094058A patent/SG186419A1/en unknown
- 2011-06-22 US US13/805,076 patent/US20130096224A1/en not_active Abandoned
- 2011-06-22 WO PCT/DK2011/050225 patent/WO2011160637A2/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| EP2585493A2 (en) | 2013-05-01 |
| US20130096224A1 (en) | 2013-04-18 |
| SG186419A1 (en) | 2013-01-30 |
| JP2013529692A (en) | 2013-07-22 |
| WO2011160637A3 (en) | 2012-02-23 |
| WO2011160637A2 (en) | 2011-12-29 |
| RU2013102587A (en) | 2014-07-27 |
| BR112012032050A2 (en) | 2016-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102947349B (en) | From the hydrophilic gel of the light trigger based on urethane | |
| CN102985447A (en) | Polyurethane based photoinitiators | |
| CN107108851B (en) | Dynamic urea linkage of polymers | |
| EP2638076B1 (en) | Novel photoinitiators | |
| JP2016047935A (en) | Polymeric photoinitiators and uses thereof | |
| CN101508853B (en) | Dual-cure coating compositions based on polyaspartates polyisocyanates and acrylate-containing compounds | |
| KR101647240B1 (en) | Polyhydroxyl - substituted amino compounds, polymers containing, and their use | |
| CN103608375B (en) | Radiation-curable polyurethane water dispersion | |
| EP2638078B1 (en) | New routes to polyacrylates | |
| JP6305631B2 (en) | Aqueous dispersion of gel particles, method for producing the same, and image forming method | |
| KR100487026B1 (en) | A process for preparing a uv cured foam | |
| CN105051012A (en) | Ethylenically unsaturated oligomers containing polymer stabilizer groups | |
| WO2016152545A1 (en) | Nail cosmetic preparation and nail-art kit | |
| JP2010180319A (en) | Urethane (meth)acrylate and coating agent containing the same | |
| CN100556928C (en) | Light sensitive polyurethane of a kind of side chain sulfur-bearing and benzophenone structural and preparation method thereof | |
| JP2021050310A (en) | Manufacturing method of aqueous urethane(meth)acrylate oligomer composition, coating composition, coated article and manufacturing method thereof | |
| JPH1180285A (en) | Polyurethane resin-based photo-curable composition | |
| US20030212207A1 (en) | Process for the solvent-free continuous preparation of a polymeric composition prepared from polymers and thermosets | |
| Wei et al. | Novel PU‐type polymeric photoinitiator comprising side‐chain benzophenone and coinitiator amine for photopolymerization of PU acrylate | |
| JP2004002854A (en) | Method for continuously producing polymer composition under condition free of solvent, this composition, and its use | |
| JPH1180665A (en) | Polyurethane resin photosetting coating agent and photosetting composition | |
| JP3353677B2 (en) | Hyperbranched compound | |
| KR940014480A (en) | Manufacturing method of water-dispersible resin and water-soluble coating composition containing same | |
| ŞABANİ | ISTANBUL TECHNICAL UNIVERSITY★ INSTITUTE OF SCIENCE AND TECHNOLOGY | |
| JP2018100358A (en) | Urethane acrylate, acrylic resin composition, cured product, and cured sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130320 |